CN110194592B

CN110194592B - Glass, glass element and optical filter

Info

Publication number: CN110194592B
Application number: CN201910555325.9A
Authority: CN
Inventors: 孙伟
Original assignee: CDGM Glass Co Ltd
Current assignee: CDGM Glass Co Ltd
Priority date: 2019-06-25
Filing date: 2019-06-25
Publication date: 2022-04-15
Anticipated expiration: 2039-06-25
Also published as: CN110194592A

Abstract

The invention provides glass, which comprises the following components in percentage by weight: p₂O₅：55～75％；Al₂O₃：2～15％；CuO：5～20％；Li₂O：1.5～15％；V₂O₅: 0.02-3%; MgO: 0 to 10 percent; BaO: 0 to 10%, wherein 10 × V₂O₅/Li₂O is 0.05 to 6.0. Through reasonable component design, the glass obtained by the invention has good transmission performance in a visible light region and good absorption performance in a near infrared region under the condition of high Cu content.

Description

Glass, glass element and optical filter

Technical Field

The invention relates to glass, in particular to glass for a near infrared light absorption filter suitable for color sensitivity correction.

Background

In recent years, the spectral sensitivity of semiconductor imaging devices such as CCDs and CMOSs used in digital cameras, mobile phones capable of taking pictures, and VTR cameras has spread to the near infrared region from the visible region to around 1100nm, and the use of a filter that absorbs light in the near infrared region can provide a visual sensitivity similar to that of humans. The visible light wavelength that can be perceived by the human eye is between 400 and 700nm, so that an image close to the luminance factor of the human eye can be obtained by using a filter that absorbs near infrared light. As the demand for color sensitivity correction filters has increased, there has been a corresponding demand for near-infrared light absorbing glasses used for manufacturing such filters, which are required to have excellent transmission characteristics in the visible region and excellent absorption characteristics in the near-infrared region.

The miniaturization and weight reduction of the photoelectric terminal products push the near infrared light absorption glass to be thinner, but if the glass is directly thinned, the near infrared light absorption performance of the glass is also reduced, and the required spectral characteristics cannot be obtained, so the content of the coloring component Cu is required to be increased to compensate the reduction of the light absorption performance caused by the thinning, and the near infrared light absorption glass has the risk of the reduction of the transmittance in the visible light region of the glass easily occurring due to the high Cu concentration.

Disclosure of Invention

For the above reasons, the present invention has been made to solve the problem of providing a near-infrared light absorbing glass having a good transmittance in the visible light region. The technical scheme adopted by the invention for solving the technical problem is as follows:

(1) glass, the composition of which, expressed in weight percent, comprises: p₂O₅：55～75％；Al₂O₃：2～15％；CuO：5～20％；Li₂O：1.5～15％；V₂O₅: 0.02-3%; MgO: 0 to 10 percent; BaO: 0 to 10%, wherein 10 × V₂O₅/Li₂O is 0.05 to 6.0.

(2) The glass according to (1), which comprises the following components in percentage by weight: na (Na)₂O: 0-8%; and/or K₂O: 0-8%; and/or CaO: 0-6%; and/or SrO: 0-6%; and/or SiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or ZnO: 0 to 5 percent; and/or Ln₂O₃: 0 to 5 percent; and/or ZrO₂: 0-6%; and/or a clarifying agent: 0 to 1% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(3) The glass according to any one of (1) or (2), wherein the components are expressed by weight percentage, and each component satisfies one or more of the following 7 cases:

1)Li₂O/Rn₂o is 0.3 to 1.0;

2) BaO/MgO is 0.2-5.0;

3)Li₂O/CuO is 0.15-2.0;

4)Na₂O+K₂o is less than 10 percent;

5)(Li₂O+CuO)/P₂O₅0.1 to 0.6;

6)10×V₂O₅/Li₂o is 0.1 to 5.0;

7) RO/CuO is less than 2.0,

wherein Rn₂O is Li₂O、Na₂O、K₂The total content of O, RO is the total content of MgO, CaO, SrO, BaO.

(4) According to any one of (1) or (2)The glass comprises the following components in percentage by weight: p₂O₅: 60-72%; and/or Al₂O₃: 3-12%; and/or CuO: 8-18%; and/or Li₂O: 2-12%; and/or V₂O₅: 0.05-2%; and/or MgO: 0.5-8%; and/or BaO: 0.5-8%; and/or Na₂O: 0 to 4 percent; and/or K₂O: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or SiO₂: 0-2%; and/or B₂O₃: 0-2%; and/or ZnO: 0-2%; and/or Ln₂O₃: 0-2%; and/or ZrO₂: 0 to 3 percent; and/or a clarifying agent: 0 to 0.5%, wherein Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(5) The glass according to any one of (1) or (2), wherein the components are expressed by weight percentage, and each component satisfies one or more of the following 7 cases:

1)Li₂O/Rn₂o is 0.5 to 1.0;

2) BaO/MgO is 0.4-3.0;

3)Li₂O/CuO is 0.2-1.0;

4)Na₂O+K₂o is less than 5 percent;

5)(Li₂O+CuO)/P₂O₅0.15 to 0.5;

6)10×V₂O₅/Li₂o is 0.2 to 2.8;

7) RO/CuO is 0.2 to 1.0,

(6) The glass according to any one of (1) or (2), which comprises, in terms of weight percent: p₂O₅: 65-72%; and/or Al₂O₃：5～11 percent; and/or CuO: 11-16%; and/or Li₂O: 3-8%; and/or V₂O₅: 0.1-1%; and/or MgO: 1-6%; and/or BaO: 1-6%; and/or Na₂O: 0-2%; and/or K₂O: 0-2%; and/or CaO: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or ZrO₂：0～2％。

(7) The glass according to any one of (1) or (2), wherein the components are expressed by weight percent, and each component satisfies one or more of the following 6 conditions:

1)Li₂O/Rn₂o is 0.7 to 1.0;

2) BaO/MgO is 0.6-2.0;

3)Li₂O/CuO is 0.3-0.8;

4)Na₂O+K₂o is less than 3 percent;

5)(Li₂O+CuO)/P₂O₅0.2 to 0.4;

6) RO/CuO is 0.3 to 0.8,

(8) The glass according to any one of (1) or (2), wherein SiO is not contained in the composition₂(ii) a And/or do not contain B₂O₃(ii) a And/or no ZnO; and/or does not contain ZrO₂(ii) a And/or does not contain CaO; and/or does not contain SrO; and/or does not contain Ln₂O₃(ii) a And/or does not contain F, wherein Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(9) The glass according to any one of (1) and (2), wherein the glass has an upper crystallization temperature of 1050 ℃ or lower, preferably 1040 ℃ or lower, more preferably 1030 ℃ or lower; and/or transition temperature T_gAt a temperature of 400 ℃ or higher, preferably 405 to 450 ℃, more preferably 410 to 440 ℃; and/or a density rho of 3.1g/cm³Hereinafter, it is preferably 3.0g/cm³Hereinafter, more preferably 2.9g/cm³The following; and/or thermal expansionCoefficient of expansion alpha_20-120℃Is 100 x 10^-7Preferably 95X 10 or less,/K^-7A value of less than or equal to K, more preferably 92X 10^-7and/K is less than or equal to.

(10) The glass according to any one of (1) and (2), wherein λ is a wavelength corresponding to a transmittance of 50% when the glass has a thickness of 0.11mm₅₀Is 620 to 650nm, preferably 625 to 645nm, and more preferably 628 to 640 nm.

(11) The glass according to any one of (1) and (2), which has a transmittance τ at 400nm of a 0.11 mm-thick glass₄₀₀72% or more, preferably 75% or more, more preferably 77% or more; and/or a transmittance at 1100nm τ₁₁₀₀Is 15% or less, preferably 12% or less, more preferably 10% or less.

The present invention also provides a glass element:

(12) a glass element comprising the glass according to any one of (1) to (11).

The present invention also provides an optical filter:

(13) an optical filter comprising the glass according to any one of (1) to (11), or comprising the glass element according to any one of (12).

The invention also provides a device:

(14) a device comprising the glass according to any one of (1) to (11), or comprising the glass element according to (12), or comprising the optical filter according to (13).

The invention has the beneficial effects that: through reasonable component design, the glass obtained by the invention has good transmission performance in a visible light region and good absorption performance in a near infrared region under the condition of high Cu content.

Detailed Description

The following describes in detail embodiments of the glass of the present invention, but the present invention is not limited to the embodiments described below, and can be implemented by making appropriate changes within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the invention is not limited to this.

The ranges of the individual components of the glasses according to the invention are explained below. In the present specification, the contents of the respective components are all expressed in terms of weight percentage with respect to the total amount of glass matter converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the glass composition component of the present invention are decomposed in the melt and converted to oxides, the total amount of the oxides is 100%.

Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B. The composition of the glass of the present invention and the present specification can be quantified by, for example, ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) or the like.

P₂O₅Is an indispensable component constituting the glass skeleton of the present invention, and can promote the formation of glass and improve the chemical stability of glass, while P₂O₅The absorption performance of the glass to near infrared light can be improved. If P₂O₅The content of (b) is less than 55%, the above effects are insufficient, and the near infrared absorption function of the glass does not meet the design requirements; if P₂O₅In excess of 75%, the devitrification tendency of the glass increases. Thus P in the invention₂O₅The content of (B) is 55 to 75%, preferably 60 to 72%, more preferably 65 to 72%.

Al₂O₃Is also a main component for forming the glass, and is used for increasing the stability of the formed glass, improving the intrinsic strength of the glass and improving the weather resistance of the glass, and the invention introduces more than 2 percent of Al₂O₃To obtain the above properties, but when Al is used₂O₃When the content exceeds 15%, the glass tends to be devitrified, and the melting property of the glass is deteriorated. Thus, Al in the invention₂O₃The content of (b) is 2 to 15%, preferably 3 to 12%, more preferably 5 to 11%。

CuO is an essential component for obtaining the near infrared absorption performance of the glass, and if the content of CuO is less than 5%, the near infrared absorption performance of the glass can hardly meet the design requirement under the condition that the glass is light and thin. In some embodiments of the present invention, by introducing more than 8% of CuO into the glass network, the chemical stability of the glass can be improved, and the thermal expansion coefficient can be reduced. However, if the content of CuO exceeds 20%, the visible light transmittance of the glass decreases, the valence of Cu in the glass changes, and it is difficult to obtain desired light absorption performance, and the devitrification resistance of the glass is low. Therefore, the content of CuO in the present invention is limited to 5 to 20%, preferably 8 to 18%, and more preferably 11 to 16%.

Li₂O is present as an essential component in the present invention, lowers the melting temperature and viscosity of the glass, and contributes more to chemical stability and mechanical strength than Na₂O and K₂O, in the present invention, 1.5% or more of Li is preferably incorporated₂And O. In some embodiments of the invention, the incorporation of more than 3% Li is carried out₂O, it is possible to prevent the valence change and the deterioration of devitrification resistance due to the introduction of a large amount of CuO. But when Li is present₂The O content exceeds 15%, and the chemical stability and formability of the glass are lowered. Thus, Li₂The lower limit of the content of O is preferably 1.5%, the lower limit is more preferably 2%, the lower limit is more preferably 3%, and Li₂The upper limit of the content of O is 15%, preferably 12%, more preferably 8%.

In some embodiments of the invention, the glass is made by including Li in the glass₂O/Rn₂The value of O is within the range of 0.3-1.0, the density of the glass can be reduced, the devitrification resistance of the glass is improved, and Li is preferably used₂O/Rn₂O has a value of 0.5 to 1.0, and Li is more preferable₂O/Rn₂The value of O is 0.7 to 1.0, and Li is more preferable₂O/Rn₂The value of O is 0.8 to 1.0. Rn₂O is Li₂O、Na₂O、K₂Total content of O, Rn in this text₂O is Li₂O、Na₂O、K₂The total content of O is Rn₂O may be represented by Li₂O、Na₂O、K₂Any one of O, or any two of O, or both of O and O contain Li₂O、Na₂O and K₂O。

In some embodiments of the invention, the lithium ion battery is prepared by reacting Li₂The value of O/CuO is more than 0.15, which can prevent the valence change and the reduction of devitrification resistance caused by the introduction of a large amount of CuO and improve the chemical stability of the glass, but when Li is used₂When the value of O/CuO exceeds 2.0, the high-temperature viscosity and transition temperature of the glass are lowered, and the striae of the glass are deteriorated. Thus Li₂The value of O/CuO is 0.15 to 2.0, preferably 0.2 to 1.0, and more preferably 0.3 to 0.8.

In some embodiments of the invention, by controlling (Li)₂O+CuO)/P₂O₅In the range of 0.1 to 0.6, the glass forming stability and the anti-devitrification performance of the glass can be improved, and the glass can obtain proper abrasion degree, preferably (Li)₂O+CuO)/P₂O₅0.15 to 0.5, more preferably (Li)₂O+CuO)/P₂O₅0.2 to 0.4.

Na₂O is a component for improving the meltability of the glass. In the present invention, Na is added₂The content of O is 8% or less, and the glass can be prevented from lowering in transition temperature while improving the chemical stability. Preferably Na₂The content of O is 4% or less, more preferably Na₂The content of O is 2% or less.

K₂O increases the transmittance of the glass in the visible light region, and when the content exceeds 8%, the stability of the glass is lowered. In some embodiments of the invention, K₂The content of O is less than 2 percent, so that the glass can obtain excellent anti-devitrification performance and chemical stability. Thus, K₂The content of O is 8% or less, preferably K₂The content of O is 5% or less, and K is more preferable₂The content of O is 2% or less.

In some embodiments of the invention, the compound is prepared by reacting Na₂O and K₂Total content Na of O₂O+K₂O is 10% or less, and the glass has a low melting temperature and excellent stability, and Na is preferred₂O+K₂O is 5% or less, more preferably Na₂O+K₂O is less than 3%.

The MgO is introduced into the glass in the invention, so that the melting temperature of the glass can be reduced and the processability of the glass can be improved, and if the introduction amount exceeds 10%, the devitrification resistance of the glass is reduced, so that the content of the MgO is less than 10%, preferably 0.5-8%, and more preferably 1-6%.

CaO is an optional component in the present invention, and by incorporating 6% or less of CaO, it is possible to reduce the high-temperature viscosity and prevent the deterioration of the devitrification resistance, and the content of CaO is preferably 5% or less, more preferably 3% or less, and further preferably no CaO.

SrO is an optional component in the present invention, and by introducing SrO of 6% or less, it is possible to prevent the deterioration of chemical stability and devitrification resistance of the glass, and the SrO content is preferably 5% or less, more preferably 3% or less, and further preferably no SrO is contained.

BaO increases the transmittance of the glass in the visible light region and improves the glass forming stability and strength of the glass, and if the content exceeds 10%, the density of the glass increases. In some embodiments of the present invention, by setting the content of BaO to 0.5% or more, the chemical stability of the glass can be improved, and the thermal expansion coefficient of the glass can be reduced. Therefore, the content of BaO is 10% or less, preferably 0.5 to 8%, more preferably 1 to 6%.

In some embodiments of the invention, by setting the value of BaO/MgO above 0.2, the glass can obtain a lower thermal expansion coefficient and excellent chemical stability, and the high temperature viscosity of the glass is improved; when the BaO/MgO value exceeds 5.0, the density of the glass increases and the processability decreases. Therefore, the BaO/MgO value is preferably 0.2 to 5.0, more preferably 0.4 to 3.0, and still more preferably 0.6 to 2.0.

In some embodiments of the present invention, the desired transition temperature and hardness of the glass can be easily obtained while ensuring a low thermal expansion coefficient by setting the value of RO/CuO to 2.0 or less, preferably 0.2 to 1.0, more preferably 0.3 to 0.8. RO is the total content of MgO, CaO, SrO, BaO, and the total content of RO herein is that RO may be expressed as any one composition, or any two compositions, or any three compositions, or contains MgO, CaO, SrO, and BaO simultaneously.

More than 0.02 percent of V is introduced into the invention₂O₅Can promote CuO in the glass to be Cu²⁺Stable existence, improves the near infrared light absorption performance of the glass, and simultaneously improves the anti-crystallization performance of the glass, if V is₂O₅The content exceeds 3%, and the absorption of the glass in the visible light region is enhanced. Thus, in the present invention V₂O₅The content of (b) is 0.02 to 3%, preferably 0.05 to 2%, more preferably 0.1 to 1%.

Through a large amount of experimental research, the inventor finds that 10 parts of V₂O₅With 1 part of Li₂The ratio of the weight content of O is 10 XV₂O₅/Li₂O is controlled within the range of 0.05 to 6.0, and the near infrared light absorption property of the glass is improved, and the decrease of the transmittance in the visible light region is suppressed, so that 10 XV₂O₅/Li₂The value of O is 0.05 to 6.0, preferably 0.1 to 5.0. Further, control 10 XV₂O₅/Li₂O is in the range of 0.2 to 2.8, and the devitrification resistance of the glass can be improved and the strength of the glass can be improved, so that 10 XV is more preferable₂O₅/Li₂O is 0.2 to 2.8.

The invention introduces proper amount of B₂O₃Can lower the glass melting temperature when B₂O₃When the content exceeds 5%, the near infrared light absorption characteristics are degraded. Thus, B₂O₃The content is 0-5%, preferably 0-2%, and more preferably no introduction.

By adding appropriate amount of SiO₂When the content of the glass exceeds 5%, the glass is deteriorated in meltability, and unmelted impurities are likely to be formed in the glass, and the near-infrared absorption characteristics of the glass are likely to be lowered. Thus SiO₂The content of (b) is 0 to 5%, preferably 0 to 2%, and more preferably no incorporation.

ZrO₂The addition of a small amount of the glass to the glass can improve the devitrification resistance of the glass,while enhancing the chemical stability of the glass. However, if the content exceeds 6%, the melting property of the glass is remarkably lowered, and the high-temperature viscosity of the glass is remarkably increased, so that an infusible material is likely to be present in the glass. Thus, ZrO₂The content is limited to 0 to 6%, preferably 0 to 3%, more preferably 0 to 2%, and further preferably not incorporated.

ZnO can reduce the transition temperature of the glass and improve the melting property of the glass, and when the content of ZnO exceeds 5 percent, the transition temperature of the glass cannot meet the design requirement, and the chemical stability tends to be reduced. Therefore, the content of ZnO is 0 to 5%, preferably 0 to 2%, and more preferably not introduced.

Ln₂O₃(Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more) can increase the refractive index of the glass and maintain low dispersion, but when Ln₂O₃When the content of (B) exceeds 5%, the melting temperature of the glass rises and the chemical stability is lowered. Thus, Ln₂O₃Is 0 to 5%, preferably 0 to 2%, and more preferably does not contain Ln₂O₃。

By introducing 0-1% of Sb₂O₃、SnO₂SnO and CeO₂One or more components in the glass are used as a clarifying agent, so that the clarifying effect of the glass can be improved, 0-0.5% of the clarifying agent is preferably introduced, and the glass has good bubble degree, so that the clarifying agent is preferably not introduced.

F can lower the melting temperature of the glass, but its introduction causes volatilization during the glass melting process, causes environmental pollution, and the glass is likely to form streaks, so the content of F is preferably 5% or less, more preferably 2% or less, and further preferably not introduced.

The term "not introduced", "not containing", "0%" as used herein means that the compound, molecule or element is not intentionally added to the glass of the present invention as a raw material; however, it is also within the scope of the present invention that certain impurities or components, which are not intentionally added, may be present as raw materials and/or equipment for producing the glass, and may be present in small or trace amounts in the final glass.

[ production method ]

The manufacturing method of the glass of the invention is as follows: the glass is produced by adopting conventional raw materials and a conventional process, carbonate, nitrate, phosphate, metaphosphate, sulfate, hydroxide, oxide and the like are used as raw materials, the prepared furnace burden is put into a smelting furnace at 1000-1200 ℃ to be smelted after being proportioned according to a conventional method, and homogeneous molten glass without bubbles and undissolved substances is obtained after clarification, stirring and homogenization, and the molten glass is cast in a mold and annealed. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.

The glass of the present invention can be shaped by well-known methods. In some embodiments, the glass described herein can be fabricated into shaped bodies including, but not limited to, sheets by various processes including, but not limited to, slot draw, float, roll, and other sheet forming processes known in the art. Alternatively, the glass may be formed by a float process or a roll process as is well known in the art.

The glass of the present invention can be produced into a sheet-like glass molded body by a method such as grinding or polishing, but the method for producing the glass molded body is not limited to these methods.

The glass of the present invention can be of any thickness that is reasonably useful.

The properties of the glass of the present invention will be described below.

< transition temperature >

Transition temperature (T) of glass_g) The test was carried out according to the method specified in GB/T7962.16-2010.

Transition temperature (T) of the glass of the present invention_g) At a temperature of 400 ℃ or higher, preferably 405 to 450 ℃, more preferably 410 to 440 ℃.

< upper limit temperature of crystallization >

Measuring the crystallization performance of the glass by adopting a gradient temperature furnace method, manufacturing the glass into a sample of 180 x 10mm, polishing the side surface, putting the sample into a furnace with a temperature gradient (5 ℃/cm), heating to 1400 ℃, keeping the temperature for 4 hours, taking out the sample, naturally cooling to room temperature, observing the crystallization condition of the glass under a microscope, wherein the highest temperature corresponding to the occurrence of crystals of the glass is the crystallization upper limit temperature of the glass.

The glass of the present invention has an upper crystallization temperature of 1050 ℃ or lower, preferably 1040 ℃ or lower, and more preferably 1030 ℃ or lower.

< Density >

The density (. rho.) of the glass was tested according to the method specified in GB/T7962.20-2010.

The glass of the present invention has a density (. rho.) of 3.1g/cm³Hereinafter, it is preferably 3.0g/cm³Hereinafter, more preferably 2.9g/cm³The following.

< coefficient of thermal expansion >

Coefficient of thermal expansion (alpha) of glass_20～120℃) The test was carried out according to the method specified in GB/T7962.16-2010.

Coefficient of thermal expansion (. alpha.) of the glass of the present invention_20～120℃) Is 100 x 10^-7Preferably 95X 10 or less,/K^-7A value of less than or equal to K, more preferably 92X 10^-7and/K is less than or equal to.

< spectral transmittance >

The spectral transmittance of the glass according to the invention is the value obtained in the manner described by means of a spectrophotometer: assuming that the glass sample has two planes parallel to each other and optically polished, light is perpendicularly incident on one parallel plane and exits from the other parallel plane, and the intensity of the exiting light is divided by the intensity of the incident light, which is the transmittance, also referred to as the external transmittance.

When the glass thickness is 0.11mm, the spectral transmittance has the characteristics shown below:

the spectral transmittance at a wavelength of 400nm is 72% or more, preferably 75% or more, and more preferably 77% or more.

The spectral transmittance at a wavelength of 1100nm is 15% or less, preferably 12% or less, more preferably 10% or less.

When the glass thickness is 0.11mm, the spectral transmittance reaches 50% of the wavelength (lambda)₅₀) The range is 620-650 nm, the preferred rangeThe wavelength range is 625-645 nm, and the preferable wavelength range is 628-640 nm.

[ glass Member ]

The glass element according to the present invention contains the above glass, and may be a thin plate-shaped glass element or a lens used in a near-infrared absorption filter, and is suitable for color correction of a solid-state imaging device, and has various excellent properties of the above glass.

The thickness of the glass element (the distance between the incident surface and the exit surface of the transmitted light) is determined by the transmittance characteristics of the element, and is preferably 0.05 to 0.5mm, more preferably 0.08 to 0.3mm, and further preferably 0.1 to 0.2mm, and the wavelength (lambda) at which the spectral transmittance is 50%₅₀) The wavelength range is 620-650 nm, the preferable range is 625-645 nm, and the more preferable wavelength range is 628-640 nm. In order to obtain such a glass device, the composition of the glass is adjusted and the glass is processed into a device having the above-mentioned thickness of spectral characteristics.

[ optical Filter ]

The optical filter according to the present invention is a near-infrared filter comprising the above glass, or comprising the above glass element and a near-infrared absorbing element optically polished on both sides, and the color correction function of the optical filter is provided by this element, and the optical filter also has various excellent properties of the above glass.

[ apparatus ]

The glass, or glass element, or optical filter of the present invention can be made into devices such as portable communication devices (e.g., mobile phones), smart wearable devices, photographic devices, camera devices, display devices, and monitoring devices by well-known methods.

Examples

< glass examples >

In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.

In this example, glasses having compositions shown in tables 1 to 3 were obtained by the above-described glass production method. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 3.

TABLE 1

TABLE 2

TABLE 3

The glasses prepared in the examples described in tables 1 to 3 were processed into glass sheets having a thickness of 0.11mm, and the spectral transmittances of the glasses of the respective examples were measured according to the test methods described above, and the results are shown in tables 4 to 6 below.

TABLE 4

Examples	1	2	3	4	5	6	7	8	9	10
											λ₅₀(nm)	628	630	627	633	635	631	637	635	626	632
τ₄₀₀(％)	78.2	76.5	77.1	80.2	79.3	80.5	81.1	84.5	82.2	79.5
											τ₁₁₀₀(％)	9.8	9.2	8.5	8.4	8.9	10.0	10.2	9.7	9.5	8.0

TABLE 5

TABLE 6

Examples	21	22	23	24	25	26	27	28	29	30
											λ₅₀(nm)	625	630	635	632	630	631	633	636	631	634
τ₄₀₀(％)	80.2	76.4	83.6	82.5	78.7	80.4	82.2	79.5	80.3	83.2
											τ₁₁₀₀(％)	8.5	9.2	8.7	10.2	10.1	9.3	9.4	9.2	8.8	11.4

< glass element example >

The glasses of examples 1 to 30 described above were used as glass elements by a method known in the art, and examples thereof include thin plate-shaped glass elements and lenses used in near-infrared absorption filters, and the like, and are suitable for color correction applications of solid-state imaging devices, and have various excellent properties of the glasses or glass products.

< Filter embodiment >

The glass and/or glass element of examples 1-30 described above was used to form an optical filter by methods known in the art, and the optical filter of the present invention has a color correction function and also has various excellent properties of the glass or glass product.

< apparatus embodiment >

The glass and/or glass element and/or optical filter of the present invention can be manufactured by well-known methods into devices such as portable communication devices (e.g., mobile phones), smart wearable devices, photographic devices, camera devices, display devices, and monitoring devices. It is also applicable to, for example, imaging devices, sensors, microscopes, medical technology, digital projection, optical communication technology/information transmission, or to imaging devices and apparatuses in the field of vehicle mounting.

Claims

1. A glass, characterized in that its composition is heavyThe weight percentage shows that the composition comprises: p₂O₅：55～75％；Al₂O₃：2～15％；CuO：5～20％；Li₂O：1.5～15％；V₂O₅: 0.02-3%; MgO: 0 to 10 percent; BaO: 0 to 10%, wherein 10 × V₂O₅/Li₂O is 0.05 to 6.0, RO/CuO is 2.0 or less, and RO is the total content of MgO, CaO, SrO, and BaO.

2. The glass according to claim 1, characterized in that it further comprises, expressed in percentages by weight: na (Na)₂O: 0-8%; and/or K₂O: 0-8%; and/or CaO: 0-6%; and/or SrO: 0-6%; and/or SiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or ZnO: 0 to 5 percent; and/or Ln₂O₃: 0 to 5 percent; and/or ZrO₂: 0-6%; and/or a clarifying agent: 0 to 1% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

3. Glass according to claim 1 or 2, characterised in that its components, expressed in weight percentage, satisfy one or more of the following 6 conditions:

1)Li₂O/Rn₂o is 0.3 to 1.0;

2) BaO/MgO is 0.2-5.0;

3)Li₂O/CuO is 0.15-2.0;

4)Na₂O+K₂o is less than 10 percent;

5)(Li₂O+CuO)/P₂O₅0.1 to 0.6;

6)10×V₂O₅/Li₂o is 0.1 to 5.0,

wherein Rn₂O is Li₂O、Na₂O、K₂The total content of O.

4. Glass according to claim 1 or 2, characterised in that its composition, expressed in weight percentage, contains: p₂O₅: 60-72%; and/or Al₂O₃: 3-12%; and/or CuO: 8-18%; and/or Li₂O: 2-12%; and/or V₂O₅: 0.05-2%; and/or MgO: 0.5-8%; and/or BaO: 0.5-8%; and/or Na₂O: 0 to 4 percent; and/or K₂O: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or SiO₂: 0-2%; and/or B₂O₃: 0-2%; and/or ZnO: 0-2%; and/or Ln₂O₃: 0-2%; and/or ZrO₂: 0 to 3 percent; and/or a clarifying agent: 0 to 0.5%, wherein Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

5. Glass according to claim 1 or 2, characterized in that its components, expressed in weight percentage, satisfy one or more of the following 7 cases:

1)Li₂O/Rn₂o is 0.5 to 1.0;

2) BaO/MgO is 0.4-3.0;

3)Li₂O/CuO is 0.2-1.0;

4)Na₂O+K₂o is less than 5 percent;

5)(Li₂O+CuO)/P₂O₅0.15 to 0.5;

6)10×V₂O₅/Li₂o is 0.2 to 2.8;

7) RO/CuO is 0.2 to 1.0,

6. Glass according to claim 1 or 2, characterised in that its composition, expressed in weight percentage, contains: p₂O₅: 65-72%; and/or Al₂O₃: 5-11%; and/or CuO: 11-16%; and/or Li₂O: 3-8%; and/or V₂O₅: 0.1-1%; and/or MgO: 1-6%; and/or BaO: 1-6%; and/or Na₂O: 0-2%; and/or K₂O: 0-2%; and/or CaO: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or ZrO₂：0～2％。

7. Glass according to claim 1 or 2, characterised in that its components, expressed in weight percentage, satisfy one or more of the following 6 conditions:

1)Li₂O/Rn₂o is 0.7 to 1.0;

2) BaO/MgO is 0.6-2.0;

3)Li₂O/CuO is 0.3-0.8;

4)Na₂O+K₂o is less than 3 percent;

5)(Li₂O+CuO)/P₂O₅0.2 to 0.4;

6) RO/CuO is 0.3 to 0.8,

8. Glass according to claim 1 or 2, characterised in that its composition does not contain SiO₂(ii) a And/or do not contain B₂O₃(ii) a And/or no ZnO; and/or does not contain ZrO₂(ii) a And/or does not contain CaO; and/or does not contain SrO; and/or does not contain Ln₂O₃(ii) a And/or does not contain F, wherein Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

9. The glass according to claim 1 or 2, wherein the glass has an upper crystallization temperature of 1050 ℃ or lower; and/or transition temperature T_gAbove 400 ℃; and/or a density rho of 3.1g/cm³The following; and/or coefficient of thermal expansion alpha_20-120℃Is 100 x 10^-7and/K is less than or equal to.

10. The glass according to claim 1 or 2, wherein the glass has an upper crystallization temperature limit of 1040 ℃ or less; and/or transition temperature T_gThe temperature is 405-450 ℃; and/or a density rho of 3.0g/cm³The following; and/or coefficient of thermal expansion alpha_20-120℃Is 95X 10^-7and/K is less than or equal to.

11. The glass according to claim 1 or 2, wherein the glass has an upper crystallization temperature of 1030 ℃ or lower; and/or transition temperature T_gIs 410-440 ℃; and/or a density rho of 2.9g/cm³The following; and/or coefficient of thermal expansion alpha_20-120℃Is 92 x 10^-7and/K is less than or equal to.

12. Glass according to claim 1 or 2, characterised in that the 0.11mm thick glass has a transmission of up to 50% at the corresponding wavelength λ₅₀Is 620 to 650 nm.

13. Glass according to claim 1 or 2, characterised in that the 0.11mm thick glass has a transmission of up to 50% at the corresponding wavelength λ₅₀625-645 nm.

14. Glass according to claim 1 or 2, characterised in that the 0.11mm thick glass has a transmission of up to 50% at the corresponding wavelength λ₅₀Is 628-640 nm.

15. Glass according to claim 1 or 2, characterised in that the transmission τ at 400nm of the glass 0.11mm thick is₄₀₀Is more than 72 percent; and/or a transmittance at 1100nm τ₁₁₀₀Is 15% or moreThe following steps.

16. Glass according to claim 1 or 2, characterised in that the transmission τ at 400nm of the glass 0.11mm thick is₄₀₀Is more than 75 percent; and/or a transmittance at 1100nm τ₁₁₀₀Is 12% or less.

17. Glass according to claim 1 or 2, characterised in that the transmission τ at 400nm of the glass 0.11mm thick is₄₀₀Is more than 77 percent; and/or a transmittance at 1100nm τ₁₁₀₀Is 10% or less.

18. A glass element comprising the glass according to any one of claims 1 to 17.

19. An optical filter comprising the glass according to any one of claims 1 to 17 or comprising the glass element according to claim 18.

20. An apparatus comprising a glass according to any one of claims 1 to 17, or comprising a glass element according to claim 18, or comprising an optical filter according to claim 19.